CN113637329A - High-biocompatibility photosensitive organic silicon material, preparation method thereof and application thereof in photocuring 3D printing - Google Patents

High-biocompatibility photosensitive organic silicon material, preparation method thereof and application thereof in photocuring 3D printing Download PDF

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CN113637329A
CN113637329A CN202110839957.5A CN202110839957A CN113637329A CN 113637329 A CN113637329 A CN 113637329A CN 202110839957 A CN202110839957 A CN 202110839957A CN 113637329 A CN113637329 A CN 113637329A
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向洪平
张蓝月
林子谦
吴瑶
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Guangdong University of Technology
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Abstract

The invention discloses a high-biocompatibility photosensitive organosilicon material and a preparation method thereof and application thereof in photocuring 3D printing, wherein photosensitive modified polydimethylsiloxane in the system has an ultraviolet light induced response o-nitrobenzyl alcohol structure, the o-nitrobenzyl alcohol structure can be quickly converted into an o-nitrobenzaldehyde structure under the induction of ultraviolet light, and aldehyde groups generated by the induction of ultraviolet light and amino groups in amino modified polydimethylsiloxane are subjected to condensation reaction to realize cross-linking molding, so that the high-biocompatibility photosensitive organosilicon material is prepared, can be directly induced to be cross-linked and cured under the ultraviolet light without a photoinitiator, and overcomes the problems of initiator residue and surface migration caused by the traditional photocuring organosilicon material requiring the photoinitiator and the biotoxicity; the photoinduced crosslinking reaction rate is high, and the photoinduced crosslinking reaction can be widely applied to photocuring 3D printing and used for preparing biomedical devices.

Description

High-biocompatibility photosensitive organic silicon material, preparation method thereof and application thereof in photocuring 3D printing
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high-biocompatibility photosensitive organic silicon material, a preparation method thereof and application thereof in photocuring 3D printing.
Background
The organic silicon material is an element organic polymer with a molecular chain having repeated Si-O-Si bonds and Si atoms connected with organic groups. Because of the advantages of no toxicity, no odor, physiological inertia, aging resistance, good air permeability, no inflammation of surrounding tissues and the like, the nano-particles are widely applied to the field of biomedicine, such as bionic tissues or organs implanted into a human body for a long time, medical instruments implanted into the human body for a short time, devices used in vitro and the like. Although the organosilicon material has become one of the most widely used medical polymer materials, the traditional vulcanization molding process of the organosilicon material is time-consuming and energy-consuming, has poor space-time controllability and lacks the possibility of continuous production, and the requirements on the functionalization and intellectualization of organosilicon material products are increasingly improved along with the development of the precision, individualization and intellectualization of biomedical materials.
The photocuring 3D printing technology is characterized in that liquid photosensitive resin is rapidly polymerized and crosslinked under UV irradiation, the liquid photosensitive resin is rapidly converted into a solid photosensitive resin, and resin materials are stacked layer by layer after curing until a 3D device is formed; the printing device has the advantages of low energy consumption, high speed, high precision, good quality and the like, and can print any device with complex structure which can not be processed by the traditional processing mode. Therefore, photocurable silicone materials prepared by introducing photocrosslinkable groups into polysiloxane molecular chains have been extensively developed and utilized. Chinese patent CN110607074A discloses a UV-moisture dual-curing organic silicon resin composition with excellent weather resistance, which comprises organic silicon resin, an organic silicon cross-linking agent, a photoinitiator and a catalyst in a certain ratio; however, because the conventional photo-curing silicone material needs to be crosslinked and formed by adding a photoinitiator, the photochemical reaction is difficult to be carried out by 100%, a large amount of photoinitiator in a cured and formed system and benzene fragments generated by the decomposition of the photoinitiator can migrate to the surface of the material to cause serious biological toxicity. In addition, although the commonly used photoinitiator 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone (Irgacure2959) is the only photoinitiator approved by the FDA, it is only used for products which are not in direct contact with food, and has the same problem of biocompatibility, so that the existing photocurable organosilicon material is difficult to be applied to the fields of biomedical treatment and the like, and the application thereof to medical materials such as in-vivo filling, medical catheters, cardiac pacemakers and the like is limited. For this reason, there is a high necessity to develop a photocurable silicone material having high biocompatibility.
Disclosure of Invention
The invention aims to solve the technical problem that the existing photocuring organic silicon material needs to use a photoinitiator, and after the photocuring organic silicon material is cured and formed, residual photoinitiator and benzene fragments generated by photolysis of the photoinitiator are transferred to the surface of the material to cause serious biological toxicity.
It is still another object of the present invention to provide a method for preparing a highly biocompatible photosensitive organosilicon material.
Another object of the present invention is to provide a use of a highly biocompatible photosensitive silicone material.
The above purpose of the invention is realized by the following technical scheme:
a photosensitive organosilicon material with high biocompatibility comprises the following components in parts by weight:
50-100 parts of photosensitive modified polydimethylsiloxane;
30-80 parts of amino modified polydimethylsiloxane;
the photosensitive modified polydimethylsiloxane is one or more of 2-nitrobenzyl alcohol based oxypropyl modified polydimethylsiloxane, (5-methoxy-2-nitro) benzyl alcohol oxypropyl modified polydimethylsiloxane and 1-nitro-2-anthracene methanol oxypropyl modified polydimethylsiloxane;
the amino modified polydimethylsiloxane is one or a mixture of more of gamma-aminopropyl modified polydimethylsiloxane, gamma-aminoethylaminopropyl modified polydimethylsiloxane or gamma-diethylenetriaminopropyl modified polydimethylsiloxane.
The photosensitive modified polydimethylsiloxane in the system has a photosensitive o-nitrobenzyl alcohol structure, the o-nitrobenzyl alcohol structure is converted into an o-nitrobenzaldehyde structure under the induction of ultraviolet light, and crosslinking is realized through condensation reaction of aldehyde groups and amino groups on the amino modified polydimethylsiloxane to prepare the photosensitive organosilicon material with high biocompatibility. In addition, the ratio of each component in the system is regulated and controlled, so that the photoinduced crosslinking reaction rate of the system meets the requirement (3-8 s) of the photocuring 3D printing technology-1) And various biomedical devices with specific structures can be rapidly prepared, and popularization and application of photocuring organic silicon materials and 3D printing technology in the medical field are facilitated.
Preferably, the composition comprises the following components in parts by weight:
70-90 parts of photosensitive modified polydimethylsiloxane;
50-70 parts of amino modified polydimethylsiloxane.
Preferably, the photosensitive modified polydimethylsiloxane is (5-methoxy-2-nitro) benzyl alcohol oxypropyl modified polydimethylsiloxane and/or 1-nitro-2-anthracene methyl alcohol oxypropyl modified polydimethylsiloxane.
Preferably, the preparation method of the photosensitive modified polydimethylsiloxane comprises the following steps:
mixing and dissolving a photosensitive monomer and hydrogen-containing polydimethylsiloxane in an equimolar manner in a solvent, adding a platinum catalyst, reacting for 3-8 h at 60-90 ℃, and removing the solvent after the reaction is finished to obtain the photosensitive modified polydimethylsiloxane, wherein the photosensitive monomer is 4-propyleneoxy-2-nitrobenzyl alcohol, 5-methoxy-4-propyleneoxy-2-nitrobenzyl alcohol or 6-propyleneoxy-1-nitro-2-anthracenemethanol.
The synthesis reaction equation of the (5-methoxy-2-nitro) benzyl alcohol oxypropyl modified polydimethylsiloxane is as follows:
Figure BDA0003175863720000031
the synthesis reaction equation of the 1-nitro-2-anthracene methanol oxypropyl modified polydimethylsiloxane is as follows:
Figure BDA0003175863720000032
preferably, the preparation method of the photosensitive monomer comprises the following steps: dissolving equimolar 3-methoxy-4-hydroxybenzaldehyde (a) and allyl bromide (b) in ethanol, and adding acid-binding agent K2CO3Stirring at room temperature for 1h to obtain K2CO3Uniformly dispersing, then keeping the temperature at 78 ℃, stirring, reacting for 16h, and purifying to obtain a product 3-methoxy-4-propenyloxybenzaldehyde (c); mixing KNO3Dispersing in trifluoroacetic acid, slowly dropwise adding 3-methoxy-4-propenyloxybenzaldehyde (c) under ice bath condition, heating to room temperature after dropwise adding, stirring for reacting for 20h, and purifying to obtain 5-methoxy-4-propenyloxy-2-nitrobenzaldehyde (d); reacting NaBH4Dissolving in ethanol, slowly dropwise adding 5-methoxy-4-propenyloxy-2-nitrobenzaldehyde (d) under an ice bath condition, heating to room temperature after dropwise adding, stirring for reacting for 4h, and purifying to obtain a photosensitive monomer 5-methoxy-4-propenyloxy-2-nitrobenzyl alcohol (e); the reaction equation is as follows:
Figure BDA0003175863720000041
mixing 2, 6-dibromoanthraquinone (a) and cesium fluoride in a molar ratio of 2: 1 is dissolved in a mixed solvent of water and DMSO, stirred for 6 hours at room temperature, and then added with an acid-binding agent K2CO3Stirring at room temperature for 2h, and purifying to obtain a product 6-bromo-2-hydroxyanthraquinone (b); reacting NaBH4Dissolving in ethanol, and slowly dripping 6-bromine under ice bath condition2-hydroxyanthraquinone (b), heating to room temperature after finishing the dropwise addition, stirring for reaction for 4 hours, and purifying to obtain a product 6-bromo-2-hydroxyanthraquinone (c); dissolving 6-bromo-2-hydroxyanthracene (c) and allyl bromide (d) in ethanol at equal molar ratio, and adding acid-binding agent K2CO3Stirring at room temperature for 1h to obtain K2CO3Uniformly dispersing, then keeping the temperature at 78 ℃, stirring, reacting for 16h, and purifying to obtain a product 6-bromo-2-propenyloxy anthracene (e); THF is used as a solvent, 6-bromo-2-acryloxyanthracene (e) and n-butyllithium in equal moles are dissolved, stirred and reacted for 2 hours at the temperature of minus 80 ℃, then DMF in equal moles is added, stirred and reacted for 1 hour at the temperature of 0 ℃, and the product 6-acryloxy-2-aldehyde anthracene (f) is obtained through purification; reacting NaBH4Dissolving in ethanol, slowly dropwise adding 6-propenyloxy-2-aldehyde anthracene (f) under an ice bath condition, heating to room temperature after dropwise adding, stirring for reaction for 4h, and purifying to obtain a product 6-propenyloxy-2-anthracene methanol (g); mixing KNO3Dispersing in trifluoroacetic acid, slowly dropwise adding 6-propylene oxy-2-anthracene methanol (g) under an ice bath condition, heating to room temperature after dropwise adding, stirring for reacting for 20h, and purifying to obtain the product 6-propylene oxy-1-nitro-2-anthracene methanol (h).
Figure BDA0003175863720000051
Preferably, the solvent is tetrahydrofuran.
Preferably, the hydrogen content of the hydrogen-containing polydimethylsiloxane is 1-4 mmol/g.
Preferably, the hydrogen-containing polydimethylsiloxane has a viscosity of 500 to 1500 cps.
Preferably, the amino modified polydimethylsiloxane is one or more of gamma-aminopropyl modified polydimethylsiloxane, gamma-aminoethylaminopropyl modified polydimethylsiloxane or gamma-diethylenetriaminopropyl modified polydimethylsiloxane.
Preferably, the preparation method of the amino modified polydimethylsiloxane comprises the following steps:
mixing aminosiloxane, octamethylcyclotetrasiloxane, hexamethyldisiloxane and deionized water, adding tetramethylammonium hydroxide as a catalyst, reacting for 4-8 h at 60-90 ℃, stirring and reacting for 2-6 h at 100-115 ℃, finally stirring and reacting for 30-60 min at 135-160 ℃ to decompose tetramethylammonium hydroxide and remove low-boiling-point substances under reduced pressure, thereby obtaining the amino modified polydimethylsiloxane.
Preferably, the aminosiloxane is one or more of gamma-aminopropylmethyldimethoxysilane, gamma-aminopropylmethyldiethoxysilane, gamma-aminoethylaminopropylmethyldimethoxysilane, gamma-aminoethylaminopropylmethyldiethoxysilane, gamma-diethylenetriaminopropylmethyldimethoxysilane or gamma-diethylenetriaminopropylmethyldiethoxysilane.
The reaction equation for preparing the amino modified polydimethylsiloxane is as follows:
Figure BDA0003175863720000061
preferably, the amino-modified polydimethylsiloxane has an ammonia value of 2 to 5 mmol/g.
Preferably, the viscosity of the amino-modified polydimethylsiloxane is 500 to 1000 cps.
The invention protects the preparation method of the photosensitive organosilicon material with high biocompatibility, which comprises the following steps:
and uniformly mixing the photosensitive modified polydimethylsiloxane and the amino modified polydimethylsiloxane to obtain the high-biocompatibility photosensitive organosilicon material.
Preferably, the mixing is uniformly stirred by a high-speed disperser.
The invention protects the application of the photosensitive organic silicon material with high biocompatibility in photocuring 3D printing.
Preferably, the method comprises the following steps:
and (3) pouring the photosensitive organic silicon material with high biocompatibility into a photocuring 3D printer, selecting a digital model, and then printing to obtain the organic silicon 3D printing device with high biocompatibility.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a high-biocompatibility photosensitive organic silicon resin, wherein photosensitive modified polydimethylsiloxane in the system has an ultraviolet light induced response o-nitrobenzyl alcohol structure, the o-nitrobenzyl alcohol structure is converted into an o-nitrobenzaldehyde structure under the induction of ultraviolet light, and crosslinking is realized through condensation reaction between aldehyde groups and amino groups on amino modified polydimethylsiloxane, so that the high-biocompatibility photosensitive organic silicon material is prepared. The photosensitive organic silicon material can be subjected to ultraviolet light induced curing under the condition of no photoinitiator, the problem of biotoxicity caused by initiator residue and surface migration in the traditional photocuring organic silicon material requiring the photoinitiator is solved, and the cured material has high biocompatibility and can be applied to medical materials; in addition, the ratio of each component in the system is regulated and controlled, so that the photoinduced crosslinking reaction rate of the system meets the rapid requirement (3-8 s) of the photocuring 3D printing technology-1) The method is combined with a photocuring 3D printing technology to rapidly prepare various biomedical devices with specific structures, and is favorable for popularization and application of photocuring organic silicon materials and the 3D printing technology in the medical field.
Drawings
FIG. 1 is a schematic diagram of a photo-curing mechanism for photosensitive silicone materials.
FIG. 2 is an infrared spectrum of amino-modified polydimethylsiloxane synthesized in example 1 and example 3.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
Example 1
A photosensitive organosilicon material with high biocompatibility comprises the following components in parts by weight:
70 parts of (5-methoxy-2-nitro) benzyl alcohol oxypropyl modified polydimethylsiloxane;
50 parts of gamma-aminoethylaminopropyl modified polydimethylsilane.
The preparation method of the high-biocompatibility organosilicon material comprises the following steps:
preparation of (5-methoxy-2-nitro) benzyl alcohol oxypropyl modified polydimethylsiloxane:
mixing and dissolving 200g of hydrogen-containing polydimethylsiloxane (1mmol/g, 1500cps) and 47.85g of 5-methoxy-4-propenyloxy-2-nitrobenzyl alcohol in 100g of tetrahydrofuran, adding 10ppm of platinum catalyst, stirring and reacting at 60 ℃ for 8h, and removing the tetrahydrofuran by reduced pressure distillation after the reaction is finished to obtain (5-methoxy-2-nitro) benzyl alcohol oxypropyl modified polydimethylsiloxane;
preparation of gamma-aminoethylaminopropyl-modified polydimethylsilane:
mixing 55.66g of gamma-aminoethyl aminopropyl methyl dimethoxy silane, 200g of octamethylcyclotetrasiloxane, 5.11g of hexamethyldisiloxane and 9.71g of deionized water, adding 0.52g of tetramethyl ammonium hydroxide, stirring and reacting at 90 ℃ for 4h, then stirring and reacting at 105 ℃ for 4h, finally stirring and reacting at 150 ℃ for 30min to decompose the catalyst and remove low-boiling-point substances under reduced pressure to obtain gamma-aminoethyl aminopropyl modified polydimethylsiloxane (2.21mmol/g, 680 cps);
and (5-methoxy-2-nitro) benzyl alcohol oxypropyl modified polydimethylsiloxane 70 parts and gamma-aminoethyl aminopropyl modified polydimethylsiloxane 50 parts are mixed and uniformly stirred by a high-speed dispersion machine to obtain the high-biocompatibility organosilicon material.
Example 2
A photosensitive organosilicon material with high biocompatibility comprises the following components in parts by weight:
80 parts of (5-methoxy-2-nitro) benzyl alcohol oxypropyl modified polydimethylsiloxane;
70 parts of gamma-aminoethyl aminopropyl modified polydimethylsiloxane.
The preparation method of the high-biocompatibility organosilicon material comprises the following steps:
preparation of (5-methoxy-2-nitro) benzyl alcohol oxypropyl modified polydimethylsiloxane:
mixing and dissolving 200g of hydrogen-containing polydimethylsiloxane (1.5mmol/g, 1000cps) and 71.77g of 5-methoxy-4-propenyloxy-2-nitrobenzyl alcohol in 100g of tetrahydrofuran, adding 10ppm of platinum catalyst, stirring and reacting at 70 ℃ for 6 hours, and removing the tetrahydrofuran by reduced pressure distillation after the reaction is finished to obtain (5-methoxy-2-nitro) benzyl alcohol oxypropyl modified polydimethylsiloxane;
preparation of gamma-aminoethylaminopropyl-modified polydimethylsilane:
69.57g of gamma-aminoethyl aminopropyl methyl dimethoxy silane, 200g of octamethylcyclotetrasiloxane, 6.73g of hexamethyldisiloxane and 12.14g of deionized water are mixed, 0.55g of tetramethyl ammonium hydroxide is added, stirring reaction is carried out at 90 ℃ for 4h, then stirring reaction is carried out at 105 ℃ for 4h, finally stirring reaction is carried out at 150 ℃ for 30min to decompose the catalyst and remove low-boiling-point substances under reduced pressure, thus obtaining gamma-aminoethyl aminopropyl modified polydimethylsilane (2.58mmol/g, 560 cps);
and (5-methoxy-2-nitro) benzyl alcohol oxypropyl modified polydimethylsiloxane 80 parts and gamma-aminoethyl aminopropyl modified polydimethylsiloxane 70 parts are mixed and uniformly stirred by a high-speed dispersion machine to obtain the high-biocompatibility organosilicon material.
Example 3
A photosensitive organosilicon material with high biocompatibility comprises the following components in parts by weight:
90 parts of 1-nitro-2-anthracenemethylol oxypropyl modified polydimethylsiloxane;
70 parts of gamma-diethylenetriaminopropyl modified polydimethylsiloxane.
The preparation method of the high-biocompatibility organosilicon material comprises the following steps:
preparation of 1-nitro-2-anthracenemethyloxypropyl modified polydimethylsiloxane:
mixing and dissolving 200g of hydrogen-containing polydimethylsiloxane (2mmol/g, 500cps) and 123.64g of 6-propyleneoxy-1-nitro-2-anthracenemethanol in 150g of tetrahydrofuran, adding 10ppm of platinum catalyst, stirring and reacting at 80 ℃ for 4 hours, and removing the tetrahydrofuran by reduced pressure distillation after the reaction is finished to obtain 1-nitro-2-anthracenemethyloxypropyl modified polydimethylsiloxane;
preparing gamma-diethylenetriaminopropyl modified polydimethylsilane:
mixing 67.26g of gamma-diethylenetriaminopropylmethyldimethoxysilane, 200g of octamethylcyclotetrasiloxane, 4g of hexamethyldisiloxane and 9.71g of deionized water, adding 0.54g of tetramethylammonium hydroxide, stirring and reacting at 90 ℃ for 4h, then stirring and reacting at 110 ℃ for 3h, finally stirring and reacting at 140 ℃ for 50min to decompose the catalyst and remove low-boiling-point substances under reduced pressure to obtain gamma-diethylenetriaminopropyl modified polydimethylsiloxane (3.17mmol/g, 860 cps);
and (2) mixing 90 parts of 1-nitro-2-anthracenemethylol oxypropyl modified polydimethylsiloxane and 70 parts of gamma-diethylenetriaminopropyl modified polydimethylsiloxane, and uniformly stirring by a high-speed dispersion machine to obtain the high-biocompatibility organosilicon material.
Example 4
The synthesis process was the same as in example 3, except that 90 parts of 1-nitro-2-anthracenemethyloxypropyl-modified polydimethylsiloxane was used; 60 parts of gamma-diethylenetriaminopropyl modified polydimethylsiloxane.
Example 5
The synthesis process is the same as that of example 3, except that 80 parts of 1-nitro-2-anthracene methanol oxypropyl modified polydimethylsiloxane is used; 70 portions of gamma-diethylenetriaminopropyl modified polydimethylsiloxane.
Comparative example 1
In the comparative example, 100 parts of acrylate modified polysiloxane and 3 parts of photoinitiator 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone (Irgacure2959) are mixed and uniformly stirred by a high-speed dispersion machine to obtain the traditional photocuring organosilicon material.
Comparative example 2
This comparative example is the same as the preparation of example 1 except that 30 parts of (5-methoxy-2-nitro) benzyloxypropyl modified polydimethylsiloxane; 50 parts of gamma-aminoethyl aminopropyl modified polydimethylsiloxane.
Comparative example 3
This comparative example was prepared in the same manner as in example 3 except that 90 parts of 1-nitro-2-anthracenemethyloxypropyl-modified polydimethylsiloxane were used; the gamma-diethylenetriaminopropyl modified polydimethylsiloxane is changed into 20 parts.
Structural characterization and Performance testing
1. Test method
(1) Biocompatibility
The biocompatibility of the photocured silicone material is studied according to the content specified in the biological evaluation standard (ISO 10993) of medical instruments, and the hemolytic compatibility of the silicone material product is tested according to the ISO 10993-4 standard; the silicone material preparations were tested for in vitro cytotoxicity according to ISO 10993-5.
(2) Rate of photocuring
And measuring the surface drying time by a finger pressing method, coating the prepared photosensitive organosilicon material on tinplate to a thickness of 100 microns, carrying out photocuring crosslinking molding by using 365nm ultraviolet light, slightly pressing the coating by fingers after exposing for a certain time, and if no indentation exists, determining that the coating is qualified, otherwise, determining that the coating is not qualified.
(3) Infrared Spectrum testing
The molecular structure of each component of the photosensitive organic silicon material is measured by a Nicolet Magna 360 Fourier transform infrared spectrometer, a KBr tabletting method is adopted, and the scanning wave number range is 500-4000 cm-1。
2. Test results
TABLE 1 Performance test results of photosensitive organosilicon materials prepared in each example and comparative example
Figure BDA0003175863720000101
Figure BDA0003175863720000111
The photosensitive organosilicon material provided by the embodiments 1-5 of the invention has excellent biocompatibility and very high photocuring rate, and can meet the requirements of photocuring 3D printing for 3-8 s-1The light curing rate can be regulated and controlled by regulating the relative content of the two components in the system; comparative example 1 preparationThe conventional free radical photo-curing organic silicon material has a fast curing speed, but has poor biocompatibility due to the use of a photoinitiator, and comparative examples 2 and 3 have excellent biocompatibility, but have slow photo-curing speed due to different proportions of the components, and cannot meet the fast forming requirement of photo-curing 3D printing.
Fig. 1 is a schematic diagram of a photo-crosslinking reaction of a photo-cured silicone material, in which an o-nitrobenzyl alcohol structure on a photosensitive modified polydimethylsiloxane in the silicone material is transited from a ground state to an excited state after absorbing photons with a specific wavelength, intramolecular charge rearrangement occurs, the o-nitrobenzyl alcohol structure is converted into an o-nitrobenzaldehyde structure, and the formed aldehyde group can rapidly undergo a condensation reaction with an amino group on an amino-modified polydimethylsiloxane to achieve crosslinking and curing.
FIG. 2 is an infrared spectrum of amino-modified polydimethylsiloxane synthesized in example 1 and example 3, which is 3296cm from FIG. 2-1The absorption peak at (B) is the stretching vibration peak of primary amino group, 1549cm-1The absorption peak is the bending vibration absorption peak of secondary amine group, 1070cm-1The absorption peak at (A) is a vibration absorption peak of Si-O-Si, indicating that the amino-modified polydimethylsiloxane was synthesized in example 1 and example 3.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

1. A photosensitive organosilicon material with high biocompatibility is characterized by comprising the following components in parts by weight:
50-100 parts of photosensitive modified polydimethylsiloxane;
30-80 parts of amino modified polydimethylsiloxane;
the photosensitive modified polydimethylsiloxane is one or more of 2-nitrobenzyl alcohol based oxypropyl modified polydimethylsiloxane, (5-methoxy-2-nitro) benzyl alcohol oxypropyl modified polydimethylsiloxane and 1-nitro-2-anthracene methanol oxypropyl modified polydimethylsiloxane;
the amino modified polydimethylsiloxane is one or a mixture of more of gamma-aminopropyl modified polydimethylsiloxane, gamma-aminoethylaminopropyl modified polydimethylsiloxane or gamma-diethylenetriaminopropyl modified polydimethylsiloxane.
2. The highly biocompatible photosensitive organosilicon material of claim 1, comprising the following components in parts by weight:
70-90 parts of photosensitive modified polydimethylsiloxane;
50-70 parts of amino modified polydimethylsiloxane.
3. The highly biocompatible photosensitive silicone material as claimed in claim 1, wherein the photosensitive modified polydimethylsiloxane is (5-methoxy-2-nitro) benzyloxypropyl modified polydimethylsiloxane and/or 1-nitro-2-anthracenemyloxypropyl modified polydimethylsiloxane.
4. The photosensitive silicone material with high biocompatibility as claimed in claim 1, wherein the preparation method of the photosensitive modified polydimethylsiloxane comprises the following steps:
mixing and dissolving a photosensitive monomer and hydrogen-containing polydimethylsiloxane in an equimolar manner in a solvent, adding a platinum catalyst, reacting for 3-8 h at 60-90 ℃, and removing the solvent after the reaction is finished to obtain the photosensitive modified polydimethylsiloxane, wherein the photosensitive monomer is 4-propyleneoxy-2-nitrobenzyl alcohol, 5-methoxy-4-propyleneoxy-2-nitrobenzyl alcohol or 6-propyleneoxy-1-nitro-2-anthracenemethanol.
5. The highly biocompatible photosensitive organosilicon material as claimed in claim 1, wherein the amino-modified polydimethylsiloxane is one or more of γ -aminopropyl-modified polydimethylsiloxane, γ -aminoethyl aminopropyl-modified polydimethylsiloxane, and γ -diethylenetriaminopropyl-modified polydimethylsiloxane.
6. The highly biocompatible photosensitive organosilicon material as claimed in claim 1, wherein the preparation method of the amino-modified polydimethylsiloxane comprises the following steps:
mixing aminosiloxane, octamethylcyclotetrasiloxane, hexamethyldisiloxane and deionized water, adding tetramethylammonium hydroxide as a catalyst, reacting for 4-8 h at 60-90 ℃, stirring and reacting for 2-6 h at 100-115 ℃, finally stirring and reacting for 30-60 min at 135-160 ℃ to decompose tetramethylammonium hydroxide and remove low-boiling-point substances under reduced pressure, thereby obtaining the amino modified polydimethylsiloxane.
7. The highly biocompatible photosensitive organosilicon material as claimed in claim 6, wherein the aminosilicone is one or more of γ -aminopropylmethyldimethoxysilane, γ -aminopropylmethyldiethoxysilane, γ -aminoethylaminopropylmethyldimethoxysilane, γ -aminoethylaminopropylmethyldiethoxysilane, γ -divinyltriaminopropylmethyldimethoxysilane or γ -divinyltriaminopropylmethyldiethoxysilane.
8. The method for preparing a highly biocompatible photosensitive organosilicon material according to any of claims 1 to 7, comprising the steps of:
and uniformly mixing the photosensitive modified polydimethylsiloxane and the amino modified polydimethylsiloxane to obtain the photosensitive organosilicon material with high biocompatibility.
9. Use of the highly biocompatible photosensitive silicone material according to any one of claims 1 to 7 in 3D printing.
10. Use according to claim 9, characterized in that it comprises the following steps:
and (3) pouring the photosensitive organic silicon material with high biocompatibility into a photocuring 3D printer, selecting a digital model, and then printing to obtain the organic silicon 3D printing device with high biocompatibility.
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